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RESEARCH PRODUCT
Are one-step aromatic nucleophilic substitutions of non-activated benzenes concerted processes?
Luis R. DomingoPatricia PérezMar Ríos-gutiérrezEduardo Chamorrosubject
Electron density010405 organic chemistryChemistryOrganic ChemistryOne-Step010402 general chemistry01 natural sciencesBiochemistry0104 chemical sciencesGibbs free energysymbols.namesakeNucleophileNucleophilic aromatic substitutionComputational chemistryIntramolecular forcesymbolsNucleophilic substitutionSingle bondPhysical and Theoretical Chemistrydescription
Aromatic nucleophilic substitution (SNAr) reactions of non-electrophilically activated benzenes have been studied within the Molecular Electron Density Theory (MEDT) at the B3LYP/6-311+G(d) computational level. These reactions, taking place through a one-step mechanism, present a high activation Gibbs free energy, ΔG≠ = 31.0 kcal mol-1, which decreases to 22.1 kcal mol-1 in the intramolecular process. A topological analysis of the electron localisation function along the reaction paths permits establishing the non-concerted nature of these SNAr reactions. A series of unstable structures, with similar electronic structures to those of Meisenheimer intermediates, are characterised. The present MEDT study makes it possible to establish that even these one-step SNAr reactions involving only two single bonds are non-concerted processes.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2019-08-28 | Organicbiomolecular chemistry |